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Highlights The crystal facets featured with facet-dependent physical and chemical properties can exhibit varied electrocatalytic activity toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) attributed to their anisotropy. The highly active exposed crystal facets enable increased mass activity of active sites, lower reaction energy barriers, and enhanced catalytic reaction rates for HER and OER. The formation mechanism and control strategy of the crystal facet, significant contributions as well as challenges and perspectives of facet-engineered catalysts for HER and OER are provided.

The efficiency of hydrogen evolution reaction (HER) electrocatalysts under acidic conditions is largely determined by the equilibrium of hydrogen adsorption/desorption on the catalyst surface. A promising strategy for enhancing the performance of multimetal‐supported HER electrocatalysts is the utilization of hydrogen spillover. However, current heterostructured catalysts often present challenges such as high interfacial transport barriers, extended reaction paths, and intricate synthesis processes. Addressing these limitations, a novel orthorhombic SrHf1−xRuxO3−δ perovskite oxide is proposed as an exemplary model for an atomic‐level configuration design strategy. This material exhibits a unique synergistic effect of multiple atomic‐level catalytic sites between Hf/Ru pairs, overcoming the aforementioned challenges. This study presents a new cooperative mechanism for HER, consisting of three steps: proton adsorption on the Hf site, hydrogen migration via a strong O‐bridge site, and H2 detachment from the Ru active site. The high conductivity and unusual charge redistribution within the Hf‐O‐Ru structure further enhance the specific acidic HER activity of SrHf1−xRuxO3−δ. This research paves the way for designing high‐performance HER catalysts for acidic media, leveraging hydrogen spillover and atomic‐scale configurations. The findings have significant implications for the development of efficient, cost‐effective, and environmentally friendly hydrogen production technologies. [ABSTRACT FROM AUTHOR]

Electrolytic water splitting is a promising path for the production of clean hydrogen when combined with green electric power, such as photovoltaic and wind power; however, the high current water electrolysis is mainly dependent on the utilization of Pt, Ru, and other expensive materials, while the transition metal-based catalysts still need improvement in electrocatalytic activity and stability. Here, we present the preparation of economic and scalable electrode materials, Nickel-Iron phosphide/Nickel foam (NiFeP/NF), with a hierarchical porous structure for overall water splitting as both the anode and cathode. An overall potential of 1.85 V for the current density of 100 mA cm−2, and a long lifetime of 700 h, were achieved by using NiFeP/NF as both the anode and cathode. The nanostructures of the composite phosphides were investigated and the spent electrode after long-term electrolysis was characterized to investigate the long-term failure mechanism of the phosphides. Surface shedding and reconstruction theories were proposed for the failure of the NiFeP/NF cathode and anode in long-term electrolysis, respectively. Furthermore, TiO2 coating was proved to be an efficient strategy to elongate the lifetime of the phosphide electrodes, which shows a slow current decline rate of 0.49 mA·cm−2 h−1. [ABSTRACT FROM AUTHOR]

[Display omitted] • The optimized V-doped FeP nanoflowers are prepared for enhanced HER. • V doping lowers d-band central position and hydrogen formation energy barrier. • V-FeP shows low overpotentials of 290 mV to deliver 1000 mA cm−2 for 24 h. • Over 100-h stability at 1000 mA cm−2 for water electrolysis is obtained. Reasonable design of hydrogen evolution reaction (HER) electrocatalyst from the perspective of electronic structure is a vital way to optimize the catalytic activity. Mono-metallic iron-based phosphates have been shown to be active toward HER, but their performance remains unsatisfactory despite their abundant reserves and low preparation cost. Here, guided by the d-band center and band structure theories, V-doped FeP nanoflower grown directly on iron foam are constructed. Combining the density functional theory (DFT) simulations with physical characterizations reveal that the enhanced HER activity is mainly attributed to the lowed d-band central position, increased water dissociation capacity, decreased hydrogen formation energy barrier and reduced charge transfer impedance. As a HER catalyst in 1 M KOH, the obtained V-FeP shows low overpotentials of ∼149, ∼246 and ∼290 mV to deliver the current densities of 100, 500 and 1000 mA cm−2 with at least 24 h. When coupled with other highly active oxygen evolution reaction (OER) catalyst (NiFe-LDH/IF), the NiFe-LDH/IF(+) || V-FeP/IF(-) pair also performs a low cell voltage and over 100-h stability at high current density of 1000 mA cm−2, which endows it a large potential in the practical electrolytic water industry. Our work may provide a reference for the enhancement of inert and low-cost HER-active iron phosphide. [ABSTRACT FROM AUTHOR]

It is of practical importance to develop efficient non‐precious metal hydrogen‐evolving catalysts for cost‐effective sustainable hydrogen production from water. In recent years, constructing single‐atomic catalysts (SACs) has been demonstrated to be an efficacious way to boost the catalytic activity of hydrogen evolution reaction (HER) catalysts, although most of them are based on noble metals. Very recently, great advances have been achieved in noble metal‐free SACs by design of compatible material systems and implementation of novel synthetic strategies, which are determinative for the amount and pattern of metallic single atoms to be anchored on the supports and consequently the electronic states and coordination environment of the atoms. This progress report summarizes perspectives of compositions of the SACs with appropriate synthetic methods, and their relationships with the HER catalytic performance. In addition, some state‐of‐the‐art technologies, for example, in situ techniques, high throughput techniques, and machine learning, are suggested to help the design, preparation, and characterization of SACs. [ABSTRACT FROM AUTHOR]

Catalysts with high atom utilization efficiency accompanied by improved reactivity and durability are highly desired. Metallic MoO2 with its small size easily agglomerates, making it difficult to use in water splitting to obtain hydrogen by electrolysis. Here, the nano‐Cu‐mediated multi‐site method is proposed to prepare ultrafine MoO2 nanoparticles (NPs) dispersed on poly(diallyldimethylammonium chloride)‐decorated reduced graphene oxide (denoted as MoO2/PDDA‐rGO). The introduction of Cu NPs increases the number of growth sites for MoO2 on the PDDA‐rGO and simultaneously promotes the growth rate of MoO2 on PDDA‐rGO. As a consequence, the resulting size of the MoO2 NPs is only 2 nm and these are evenly dispersed on PDDA‐rGO. Significantly, the optimized catalyst has a low onset potential of −42 mV versus reversible hydrogen electrode (RHE), a calculated Tafel slope of only 42 mV dec−1, and good cycling stability of more than 40 h. This favored hydrogen evolution reaction (HER) activity is caused by the synergistic effects of MoO2 and PDDA‐rGO, rapid charge transport, and sufficient exposed active sites of MoO2/PDDA‐rGO. Feeling fine: A nano‐Cu‐mediated multi‐site method is proposed to prepare ultrafine MoO2 nanoparticles (NPs) dispersed on poly(diallyldimethylammonium chloride)‐decorated reduced graphene oxide (MoO2/PDDA‐rGO). The optimized catalyst has an onset potential as low as −42 mV vs. RHE, a calculated Tafel slope of only 42 mV dec−1, and good cycling stability of more than 40 h. [ABSTRACT FROM AUTHOR]

Abstract: Highly efficient and precious metal free catalysts for the hydrogen evolution reaction (HER) are of vital importance for renewable energy technologies. Nevertheless, developing simple methods for the synthesis of highly active and super‐durable electrocatalysts at low cost for HER still remains a major challenge. In this work, high temperature pyrolysis of (NH4)6Mo7O24 ⋅ 4H2O, NaH2PO4 and multi‐walled carbon nanotubes (MWCNTs) in Ar atmosphere is carried out to obtain phosphorus dually doped MoO2 nanosheets (MoO2 NSs) and MWCNTs hybrids (MoO2Px NSs/P‐MWCNTs), which can serve as excellent electrocatalyst for HER. In 0.5 M H2SO4, the hybrid material catalyzes HER with an onset potential of −27 mV (vs. reversible hydrogen electrode, RHE), Tafel slope of 45 mV dec−1, and an overpotential at 10 mA cm−2 of only 57 mV. Additionally, it displays favorable stability over 50 h in acidic media. [ABSTRACT FROM AUTHOR]

Abstract: A highly efficient and pH‐universal hydrogen evolution reaction (HER) electrocatalyst with a sandwich‐architecture constructed using zero‐dimensional N‐ and P‐dual‐doped core–shell Co2P@C nanoparticles embedded into a 3 D porous carbon sandwich (Co2P@N,P‐C/CG) was synthesized through a facile two‐step hydrothermal carbonization and pyrolysis method. The interfacial electron transfer rate and the number of active sites increased owing to the synergistic effect between the N,P‐dual‐doped Co2P@C core–shell and sandwich‐nanostructured substrates. The presence of a high surface area and large pore sizes improved the mass‐transfer dynamics. This nanohybrid showed remarkable electrocatalytic activity toward the HER in a wide pH range with good stability. The computational study and experiments revealed that the carbon atoms close to the N and P dopants on the shell of Co2P@N,P‐C were effective active sites for HER catalysis and that both Co2P and the N,P dopants gave rise to an optimized binding free energy of H on the active sites. [ABSTRACT FROM AUTHOR]

Here, a facile one-pot hydrothermal method is used to synthesize multi-walled carbon nanotubes (MWCNTs) coated Mo x W 1 − x S 2 hybrid (MWCNTs@Mo x W 1 − x S 2 ). Ultimately, we obtained a material with MWCNTs evenly wrapped by Mo x W 1 − x S 2 . After studying a series of the MWCNTs@Mo x W 1 − x S 2 with different loading amounts and various mole ratios of molybdenum (Mo) and tungsten (W), we found the MWCNTs@Mo 0.54 W 0.46 S 2 (77.3 wt. % Mo 0.54 W 0.46 S 2 content) exhibited the best activity in the hydrogen evolution reaction (HER). Electrochemical experiments testified that this catalyst propelled the HER with an onset potential lowered to – 0.15 V vs. RHE, large cathode currents and a Tafel slope of ∼68 mV per decade in 0.5 M H 2 SO 4 electrolyte. Moreover, it was highly enduring in a corrosive acidic solution since the current density of this compound minished a little even if it was cycled 1000 circulations. These findings proved that the MWCNTs@MoxW 1 − x S 2 was a productive material for the generation of catalysts involving an abundant transition metal, therefore indicated a promising future in the hydrogen economy. [ABSTRACT FROM AUTHOR]

Design and synthesis of non-precious-metal catalyst for efficient electrochemical transformation of water to molecular hydrogen in acid environments is of paramount importance in reducing energy losses during the water splitting process. Here, the hybrid material of MoS 2 -coated Cu loaded on the multi-walled carbon nanotubes (MWCNTs@Cu@MoS 2 ) was synthesized using chemical process and hydrothermal method. It was found that the participation of MWCNTs and Cu nanoparticles not only improved the electrical conductivity of the catalyst, but also further enhanced the catalytic activity by synergistic effect with edge-exposed MoS 2 -coating. Electrochemical experiments demonstrated that the catalyst exhibited excellent hydrogen evolution reaction (HER) activity with large cathode currents (small overpotential of 184 mV for 10 mA cm −2 current density) and a Tafel slope as small as 62 mV per decade. Furthermore, it was discovered that the current density of this composite catalyst had a little decrease after the continual 1000 cycling, which showed the catalyst had a high stability in the recycling process. These findings confirmed that this catalyst was a useful and earth-abundant material for water splitting. [ABSTRACT FROM AUTHOR]

The process of water splitting by using efficient non-precious-metal catalyst to make the process economically viable has brought forward an extensive research. In this study, the composite of Cu and MoS 2 on the reduced graphene oxide (rGO) (Cu–MoS 2 /rGO) with high catalytic activity toward hydrogen evolution reaction (HER) was easily synthesized using hydrothermal method and chemical process. It was found that the participation of rGO improved the electrical conductivity of the catalyst, and the MoS 2 nanoflowers (NFs) with a higher number of exposed edges exhibited higher HER activity. In addition, the addition of Cu particles could not only enhance the electrical conductivity of the catalyst, but also further improved the catalytic activity by synergistic effect with MoS 2 NFs. Electrochemical experiments demonstrated that the catalyst exhibited excellent HER activity with large cathode currents and a Tafel slope as small as 90 mV decade −1 . Furthermore, it was discovered that the current density of this composite catalyst had a little decrease after the continual 700 cycling, which showed the catalyst had a high stability in the recycling process. These findings confirmed that this catalyst was a useful and earth-abundant material for water splitting. [ABSTRACT FROM AUTHOR]

[Display omitted] • F is well doped into FeP nanobelt arrays by room temperatures immersion method. • The optimized F-FeP nanobelt arraypossess enhanced HER catalytic activity. • The low overpotentials of 302 mV at 1000 mA cm−2 has been achieved. • The stability test of overall water splitting can last 100 h at 1000 mA cm−2. • DFT and UPS consistently reveal that F doping can lower the d-band center. Modulating the intrinsic activity of transition metal iron-based phosphates though tailoring d-band center has been effective strategy especially for large-scale hydrogen production at high current density. Herein, nonmetallic fluorine atoms are well doped into FeP nanobelt arrays by room temperatures immersion method for enhanced performance of hydrogen evolution reaction (HER) in alkaline solution. Significantly, the optimized fluorine-doped iron phosphide nanobelt array (3F-FeP) possess enhanced HER catalytic activity with low overpotentials of 191, 261 and 302 mV to achieve the 100, 500 and 1000 mA cm−2. Furthermore, the long-time stability test indicates that the NiFe-LDH/IF(+)//3F-FeP/IF(−) couple can last for more than 100 h at high current density of 1000 mA cm−2, which gives it a great potential in the practical electrolytic water industry. Density functional theory (DFT) calculations and ultraviolet photoemission spectroscopy (UPS) characterization consistently reveal that the doping of F can effectively regulate the electronic structure, promote electron transport, lower the d-band center position, optimize the hydrogen adsorption energy, reduce the water splitting energy and the H 2 formation energy of iron phosphate. This work can provide a facile method for the designing strategy of materials with higher catalytic activity for HER. [ABSTRACT FROM AUTHOR]

[Display omitted] A new type of self-supporting multi-channel Janus carbon fibers with efficient water splitting has been successfully manufactured using a specially designed parallel spinneret through electrospinning technology and subsequent carbonization technique. Every single Janus fiber composes of a half side of Mo 2 C and the other half side of Ni components as Mo 2 C, Ni embedded in N -doped multi-channel Janus carbon fibers ([Mo 2 C/C]//[Ni/C]-NMCFs) for overall water splitting. Under optimized condition, the hydrogen evolution reaction overpotential of [Mo 2 C/C]//[Ni/C]-NMCFs (62 mV) is just 24 mV higher than 20 wt% Pt/C (38 mV) at a current density of 10 mA cm−2. Furthermore, it achieves current density of 10 mA cm−2 to require an overpotential of 324 mV for oxygen evolution reaction. Additionally, the cell assembled by the identical [Mo 2 C/C]//[Ni/C]-NMCFs catalyst as both the cathode and anode needs only 1.607 V at a current density of 10 mA cm−2, which is only 0.022 V higher than that of Pt/C-IrO 2 electrodes. Moreover, [Mo 2 C/C]//[Ni/C]-NMCFs catalyst also exhibits a long-term stability. The synergistic effect and unique heterostructure of Mo 2 C and Ni enhance the catalytic activity. [ABSTRACT FROM AUTHOR]

Transition metal hydroxides for hydrogen evolution reaction (HER) usually have been limited by poor intrinsic activity and weak conductivity. In our work, in situ electro-oxidation as an effective way has been used to modulate the electronic states of active sites for ruthenium hydroxides, which provides obviously enhanced activity for HER in alkaline media. Ag-modified nickel foam (NF) as substrate can provide the excellent conductivity to improve the charge transfer rate of Ru(OH) x /Ag/NF. In situ electro-oxidation process has been conducted for Ru(OH) x /Ag/NF through OER measurements in alkaline media, which results in the formation of more Ru (IV) as higher actives sites for HER. Compared to Ru(OH) x /NF, X-ray photoelectron spectroscopy (XPS) and polarization curves prove that Ag doping in Ru(OH) x /Ag/NF may contribute to the oxidization of ruthenium from Ru (III) to Ru (IV) during in situ electro-oxidation. The obtained Ru(OH) x /Ag/NF exhibits Pt-like HER activity with a very low overpotential of 103.2 mV to drive 100 mA cm−2 in 1.0 M KOH. The excellent stability of Ru(OH) x /Ag/NF has also been demonstrated. Therefore, our work provides a new strategy by modulating valence state of active sites for transition metal hydroxides for efficient HER. Image 1 • Ru(OH) x /Ag/NF was prepared by in situ electro-oxidation process. • Ag doping contributes to the oxidization of ruthenium from Ru (III) to Ru (IV). • Ru(OH) x /Ag/NF exhibits Pt-like HER activity and good stability. • In situ electro-oxidation is an effective way to modulate the electronic states of active sites. [ABSTRACT FROM AUTHOR]

Abstract A Ni and Mo x C hybrid (Ni-Mo x C) supported on N-doped reduced graphene oxide (N-rGO) electrocatalyst with high hydrogen evolution reaction (HER) activity was prepared by ultrasonication and lyophilization. Notably, benefiting from the synergistic effect between Ni and Mo x C nanoparticles, the optimized electrocatalyst displayed excellent catalytic activity with low overpotentials of 183 mV and 216 mV for the HER at the current density 10 mA cm−2 in 1.0 M KOH and 0.5 M H 2 SO 4 solution. The stability of the electrocatalyst could be well maintained for 24 h. These results indicate that the method to prepare hybrid (Ni-Mo x C) is a simple way to produce cost-effective and high-efficient molybdenum carbide for hydrogen evolution. Highlights • Effective electrocatalysts with a Ni-Mo x C/N-rGO format were successfully prepared by a simple method. • The introduction of Ni is beneficial to the formation of γ-MoC in Ni-Mo x C/N-rGO. • Mo 2 C NPs/N-rGO improves HER activity synergistically with Ni. • The catalysts exhibit good HER activity in alkaline and acidic electrolytes. [ABSTRACT FROM AUTHOR]

The catalytic activity of noble-metal nanoparticles (NPs) often has closely connection with their sizes and geometric shape. In the work, polyhedral NPs of palladium (Pd) with controlled sizes, shapes, and different proportions of {100} to {111} facets on the surface were prepared by a seed-mediated approach. Electrochemical experiment demonstrates that the catalytic performance of the Pd nanocubes (NCs) enclosed by {100} facets is more active than Pd octahedrons enclosed by {111} facets for the hydrogen evolution reaction (HER), which is consistent with density functional theory (DFT) calculation results. Meanwhile, with the assistance of a polyethyleneimine–reduced graphene oxide (PEI–rGO) support, the examined Pd cube/PEI–rGO 50:1 (10 wt. %) electrocatalyst presents outstanding HER activity comparable with that of commercial Pt/C catalyst. This correlation between the HER catalytic activity and surface structure will contribute to the reasonable design of Pd catalysts for HER with high efficiency and low metal loading. [ABSTRACT FROM AUTHOR]

In this study, Ni–S–Co electrode with the microstructure of multi-channel coral-forest morphology was prepared by gradient electrodeposition. The composition of deposits was determined by XRD and XPS; the structure was characterized by SEM, TEM and EDS; the electrochemical performance and stability of Ni–S–Co electrode were studied by LSV, CV and EIS in 1 M KOH solution. Through investigating the electrode surface micromorphology and composition and evaluating various electrochemical properties of the electrode, it can be confirmed that, because of the employment of gradient electrodeposition method and the addition of Co element, the Ni–S–Co electrode surface contents was amorphous and doped with a small amount of crystalline sulfide to accelerate the efficiency of electron transfer, it also has hierarchical structure to facilitate hydrogen and electrolyte transfer. Particularly, the electrochemical surface area (ECSA) of Ni–S–Co deposits was 38405 cm2, which was extremely higher among all other reported electrodes. Moreover, Ni–S–Co deposits only requires an overpotentials of 211 mV vs. RHE to achieve a current density of 100 mA cm−2. Finally, after electrochemical stability test for 5000 cycles of CV test, the electrocatalytic properties did not decrease considerably at all, but got improved slightly. • Gradient electrodeposition enhances HER on the Ni–S–Co electrode. • Satisfying HER is due to the morphology of extremely higher ECSA. • Smooth HER is related to the multi-channel coral-forest morphology. • Improved HER after CA and CV tests confirms possible application. [ABSTRACT FROM AUTHOR]

The design and fabrication of efficient Pt-based electrocatalysts with ultralow-loading but high-mass-activity for hydrogen evolution reaction (HER) in alkaline media is of significant importance. Herein, we report the monodispersed platinum nanoparticles (PtNPs) with an ultralow Pt loading (3.6 μg per electrode area (cm2)) embed in Ni 3 S 2 -containing hollow carbon spheres as HER catalysts. Notably, the as-prepared electrocatalyst exhibits a mass activity of 7.6 A g Pt −1 at an overpotential of 70 mV, which is 8.5 times higher than that of commercial Pt/C and is among the highest levels of reported Pt-based HER electrocatalysts in alkaline conditions. This electrocatalyst also exhibits excellent HER performance with an overpotential of 42 mV reaching an area current of 10 mA cm−2 and significantly improved stability. The outstanding HER performance is attributed to the hollow and porous carbon spherical structure, as well as highly dispersed PtNPs that provide more active sites and facilitate proton/electron transport. Meanwhile, the nickel-containing layered precursors convert to some Ni 3 S 2 NPs which guarantees the formation of Pt-Ni 3 S 2 heterostructures on the carbon substrate and thus further enhance the activity of PtNPs. This work provides an effective strategy to simultaneously regulate the nanostructure and active site of Pt-containing carbon-based HER electrocatalysts. Image 1 • PtNPs embedded in Ni 3 S 2 -containing hollow carbon spheres was synthesized. • The material exhibits superior HER activity with mass activity of 7.6 A g Pt −1. • The hollow carbon spherical structure promotes the exposure of active sites. • The monodispersed PtNPs increases the atom utilization of Pt. • The highly-dispersed Pt-Ni 3 S 2 heterostructure promotes the HER kinetics. [ABSTRACT FROM AUTHOR]

[Display omitted] • The structure is stable at room temperature, and the conductivity is good, the material is cheap and easy to get. • The intrinsic active site, without the need to create an active site through vacancy defects. • Small strain can achieve ideal HER catalytic activity. The discovery of electro-catalysts for hydrogen evolution reaction (HER) with high activity and low cost has always attracted intensive attentions. Here, we propose a two-dimensional ZnCS 3 monolayer as a good HER electro-catalysts through first-principles calculations. The Gibbs free energy variation (ΔG H) of ZnCS 3 is as low as 0.123 eV, and the good HER activity is mainly due to the active dangling bond on S atoms at the surface, as well as the metallic band characteristic and excellent electrical conductivities before and after the adsorption of H atom. Moreover, we find that ΔG H could be further tuned to be 0 by applying a small tensile strain of 1.7 %, which could be understood by the evolution of p-band center of the S atom under different strains. All these results suggest that ZnCS 3 nanosheet is a promising candidate of HER electro-catalysts. [ABSTRACT FROM AUTHOR]

Electrochemical water splitting is an efficient approach to produce green hydrogen, while it is still very challenging to design of highly efficient WO 3 -based hydrogen evolution reaction (HER) catalysts especially those in neutral media. Here, 3D WO 3 /C nanoarchitectures assembled by 1D nanowires were prepared through water-oil two-phase microemulsion method and subsequent annealing treatment. The monodispersed Pt nanoparticles were loaded onto the WO 3 /C nanoarchitectures. A series of WO 3 /C composites were produced via modulating the addition of Pt salt. The optimum 2 Pt@WO 3 /C catalyst exhibited an overpotential of 149 mV at 10 mA cm−2 in neutral media, which was the first reported about the WO 3 -based materials and much better than most catalysts reported in literatures by far. Interestingly, the HER activity of 2 Pt@WO 3 /C was much higher than commercial Pt/C at high overpotential range (>260 mV). Density functional theory results demonstrated that the more toilless HER process could be attributed to the enhanced carrier densities, the electron transfer between Pt and W atoms, and the lowered energy barrier for water dissociation and H* desorption. [Display omitted] • WO 3 /C nanoarchitecture assembled by 1D nanowires was prepared via a two-phase method. • A series of Pt@WO 3 /C were developed via optimizing the addition of Pt salt and WO 3 /C. • The optimized 2 Pt@WO 3 /C delivered an overpotential of 149 mV in neutral media. • The HER activity of 2 Pt@WO 3 /C was much better than commercial Pt/C over 260 mV. • The enhanced reason was revealed by electronic structures and energy barrier diagram. [ABSTRACT FROM AUTHOR]

• Ni-S-Mn deposits by gradient electrodeposition is of mixed crystals. • Crystalline MnS is identified firstly to enhance electrode conductivity. • Sulfide framework cooperates with amorphous Ni to promote HER. • Extraordinary ECSA and better conductivity guarantees stable HER. A novel Ni-S-Mn electrode with hierarchical porous morphology of multi-channel wind-erosion-gully was fabricated through gradient electrodeposition. XRD and XPS were adopted to investigate chemical composition and elemental valence states; SEM, TEM and EDS were employed to characterize morphology and microstructure; LSV, CV and EIS were used to study electrocatalytic properties and stability of Ni-S-Mn electrode. The characterization of microstructure combined with the evaluation of electrocatalytic performances proved that the Ni-S-Mn electrode surface composition are of hierarchical porous morphologies, including the crystalline Ni 3 S 2 and MnS flake structure as framework and the amorphous Ni as intergranular fillings; electron transfer efficiency can be effectively accelerated by crystalline sulfide; the layered structure of electrode surface facilitates the mass transfer of hydrogen molecules and electrolyte solution during hydrogen evolution reaction (HER). Particularly, the as-fabricated Ni-S-Mn electrode has a remarkable electrochemical surface area (ECSA) of 43180 cm2, that is extremely higher among all other Ni-based electrode fabricated by electrodeposition. In addition to its excellent electrochemical stability confirmed by chronoamperometry (CA) at −100 mV vs. RHE for 15 h, the current density of Ni-S-Mn deposits on this novel electrode can reach as high as 713.8 mA cm−2 at an overpotential of 0.4 V vs. RHE. [ABSTRACT FROM AUTHOR]